Method for manufacturing SOI substrate

ABSTRACT

The object of the invention is to provide a method for manufacturing an SOI layer which is devoid of damages, has a reduced variation in thickness, and is uniform in thickness. The object is met by providing a method for manufacturing an SOI substrate comprising the steps of forming an oxide film at least on one surface of a first silicon substrate, implanting hydrogen ions from the surface of the first silicon substrate thereby forming an ion-implantation zone in the interior of the first silicon substrate, bonding the first silicon substrate over a second silicon substrate with the oxide film interposed thereby forming a laminated assembly, subjecting the laminated assembly to a first heating treatment consisting of heating at a specified temperature, so that the first silicon substrate is split at the ion-implantation zone thereby manufacturing a bonded substrate, flattening the exposed surface of the SOI layer by subjecting the bonded substrate to wet etching, subjecting the bonded substrate to a second heating treatment consisting of heating at 750 to 900° C. in an oxidative atmosphere thereby reducing damages inflicted to the SOI layer, and subjecting the resulting bonded substrate to a third heating treatment consisting of heating at 900 to 1200° C. thereby enhancing the bonding strength of the bonded substrate.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application claims priority of Japanese Application No. 2005-025802filed Feb. 4, 2005, the entire disclosure of which is herebyincorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method for manufacturing an SOI(silicon on insulator) substrate wherein an SOI layer is formed on anoxide film using hydrogen ion-implantation technique.

2. Description of the Related Art

A method has been proposed for manufacturing an SOI substrate (forexample, see Patent Document 1). The method comprises forming an oxidefilm on a surface of a first silicon substrate, implanting a highconcentration of hydrogen atoms into the interior of the siliconsubstrate to form an ion-implantation zone at a specified depth from thesurface of the substrate, bonding the first silicon substrate over asecond silicon substrate to form a laminated assembly, heating thelaminated assembly to 500° C. or higher, thereby separating the firstsubstrate assembly from the second substrate assembly with the hydrogenion-implantation zone at a boundary, and forming a semiconductor SOIlayer on a surface of the second substrate. According to this method, itis possible to manufacture an SOI substrate comprising a second siliconsubstrate, an oxide film formed thereon and serving as a buried oxidefilm, and a semiconductor SOI layer formed on the top of the oxide film.

However, according to the conventional method described above formanufacturing an SOI substrate, the first silicon substrate is separatedat the hydrogen ion-implantation zone, and thus the resulting SOIsubstrate suffers from crystal defects on the cleaved face. To solvethis problem, a treatment consisting of removing a superficial layerhaving crystal defects from the cleaved face was suggested, and, as oneof such treatments, a CMP (chemical mechanical polishing) method wasproposed.

Patent Document 1: Japanese Unexamined Patent Application PublicationNo. 5-211128 (claims)

According to the aforementioned conventional method for manufacturing anSOI substrate, ions forming the hydrogen ion-implantation zone containreactive ions that may have a damaging effect on the resulting SOIlayer. Namely, since the reactive ions serve as an etchant and etch thesurface of the SOI layer formed on the oxide film by the heat treatmentfor separating the first silicon substrate at the ion-implantation zone,they will inflict damage on the SOI layer, and particularly on itssuperficial layer which remains a problem to be solved. In addition, inthe conventional CMP method, it is impossible to maintain the uniformityof the thickness over the entire surface of the SOI layer, because theentire layer is turned into a thin membrane at one time. Also, theamount removed from the SOI layer surface is not necessarily uniform. Ifthe initial thickness of the SOI layer shows a variation over the entirelayer, the variation may cause the degraded uniformity over the entirelayer.

SUMMARY OF THE INVENTION

The object of the present invention is to provide a method formanufacturing an SOI substrate whereby it is possible to manufacture anSOI substrate in which the crystal integrity of the SOI layer is notseriously damaged, and the variation in thickness of the SOI layer iseffectively suppressed, i.e., the thickness of the SOI layer becomesuniform.

As shown in FIG. 1, a first aspect of the present invention as describedin claim 1 relates to a method for manufacturing an SOI substratecomprising the steps of forming an oxide film 21 at least on one surfaceof a first silicon substrate 14, implanting hydrogen ions from thesurface of the first silicon substrate 14 thereby forming anion-implantation zone 16 in the interior of the first silicon substrate14, bonding the first silicon substrate 14 over a second siliconsubstrate 12 with the oxide film 21 interposed thereby forming alaminated assembly 15, subjecting the laminated assembly 15 to a firstheating treatment consisting of heating at a specified temperature, sothat the first silicon substrate 14 is split at the ion-implantationzone 16 thereby manufacturing a bonded substrate 18 in which a thin SOIlayer 13 is formed on the second silicon substrate 12 with the oxidefilm 21 interposed, flattening the exposed surface of the SOI layer 13by subjecting the bonded substrate 18 to wet etching, subjecting thebonded substrate 18 to a second heating treatment consisting of heatingat 750 to 900° C. in an oxidative atmosphere thereby reducing damagesinflicted to the SOI layer 13, and subjecting the resulting bondedsubstrate 18 to a third heating treatment consisting of heating at 900to 1200° C. thereby enhancing the bonding strength of the bondedsubstrate 18.

According to the method described in claim 1 for manufacturing an SOIsubstrate, since the exposed surface of the SOI layer 13 is flattened bywet etching, it is possible not only to remove damages present on thesurface of the SOI layer 13 coincident with the exposed surface of theion-implantation zone 16 where the damages occur as a result of thefirst heating treatment, but also to avoid inflicting additional damagesonto the exposed surface of the SOI layer 13, thereby reducing thevariation in thickness of the SOI layer 13, and enhancing the uniformityof thickness of the SOI layer 13.

Furthermore, according to the method described in claim 1 formanufacturing an SOI substrate, since the bonded substrate 18 issubjected to the second heating treatment consisting of heating at 750to 900° C. in an oxidative atmosphere, it is possible to reduce damagesinflicted to the SOI layer 13. More specifically, the superficial layerof the SOI layer which abounds with damages as a result of hydrogenion-implantation is subjected to oxidation, and, as a consequence, thedamaged superficial layer turns into an SiO₂ film (oxide film) which canbe removed by being dissolved in an HF solution. Moreover, according tothe method of the invention, since wet etching is introduced before thesecond heating treatment, the thickness of the SOI layer 13 is smallerthan would be observed if the second heating treatment is undertakenwithout prior wet etching, and thus reduction of damages of the SOIlayer 13 can be achieved in a shorter period of time. According to theinventive method, the second heating treatment is introduced prior tothe third heating treatment which is undertaken to enhance the bondingstrength of the bonded substrate. This is because if the bondedsubstrate is subjected directly to an oxidative heating treatmentconsisting of heating to 900° C. or higher, damages still left in theSOI layer combined with interstitial silicon atoms occurring as a resultof the oxidation of silicon will cause the generation of crystal defectssuch as dislocations which will in turn degrade the crystal structure ofthe SOI layer 13 of the SOI substrate 11. In particular, if the bondedsubstrate is subjected directly to a heating treatment consisting ofheating to 900° C. or higher, the oxidation reaction proceeds at such ahigh speed that a large number of interstitial silicon atoms willdevelop in a short period of time which will then increase the incidenceof crystal defects. On the contrary, if the second heating treatmentconsisting of heating to a lower temperature, i.e., 900° C. or lower iscarried out prior to the third heating treatment, the development ofcrystal defects such as dislocations which would be generated if thethird heating treatment consisting of heating to 900° C. or higher isperformed without the second heating treatment can be safely avoided.Thus, introduction of the second treatment reduces the damage to the SOIlayer 13, and prevents degradation of the crystal structure of the SOIlayer 13.

The amount removed due to wet etching and the duration of the secondheating treatment relate with each other in terms of the quality of theresulting SOI substrate, and their relative contributions in the productof an SOI substrate 11 is determined by the nature of the requiredquality of the SOI substrate. If the requirement for the high uniformityof the thickness of the SOI layer 13 is emphasized rather than on thequality of the crystal structure of the SOI layer 13, the duration ofthe second heating treatment should be emphasized at the expense of theamount removed by the wet etching. On the contrary, if the requirementfor the high quality of the crystal structure of the SOI layer 13 isemphasized rather than for the uniformity of the thickness of the SOIlayer 13, the amount by the wet etching should be emphasized at theexpense of the uniformity of the thickness of the SOI layer 13. This isbecause wet etching is suitable for the crystal structure of the SOIlayer 13 while oxidative treatment (the second heating treatment) issuitable for the uniformity of thickness of the SOI layer 13.

A second aspect of the present invention as described in claim 2 relatesto a method for manufacturing an SOI substrate comprising the steps offorming an oxide film 21 at least on one surface of a first siliconsubstrate 14, implanting hydrogen ions from the surface of the firstsilicon substrate 14 thereby forming an ion-implantation zone 16 in theinterior of the first silicon substrate 14, bonding the first siliconsubstrate 14 over a second silicon substrate 12 with the oxide film 21interposed thereby forming a laminated assembly 15, subjecting thelaminated assembly 15 to a first heating treatment consisting of heatingat a specified temperature, so that the first silicon substrate 14 issplit at the ion-implantation zone 16 thereby manufacturing a bondedsubstrate 18 in which a thin SOI layer 13 is formed on the secondsilicon substrate 12 with the oxide film 21 interposed, subjecting thebonded substrate 18 to a second heating treatment consisting of heatingat 750 to 900° C. thereby reducing damages inflicted to the SOI layer13, and subjecting the resulting bonded substrate 18 to a third heatingtreatment consisting of heating at 900 to 1200° C. thereby enhancing thebonding strength of the bonded substrate 18.

The method described in claim 2 for manufacturing an SOI substrate issuitable for the manufacture of SOI substrates 11 for which therequirement for the uniformity of the thickness of the SOI layer 13 ismore emphasized rather than for the quality of the crystal structure ofthe SOI layer 13. In the manufacture of SOI substrates according to themethod described in claim 2, since the second treatment consisting ofheating to a comparatively low temperature, i.e., 900° C. or lower isintroduced prior to the third heating treatment consisting of heating to900° C. or higher, it is possible to prevent residual damage in the SOIlayer 13 from developing into crystal defects such as dislocations, andrather to eliminate such residual damages in SOI layer 13 therebyeffectively preventing the deterioration of crystal structure of the SOIlayer 13.

A third aspect of the present invention as described in claim 3 relatesto a method for manufacturing an SOI substrate comprising the steps offorming an oxide film 21 at least on one surface of a first siliconsubstrate 14, implanting hydrogen ions from the surface of the firstsilicon substrate 14 thereby forming an ion-implantation zone 16 in theinterior of the first silicon substrate 14, bonding the first siliconsubstrate 14 over a second silicon substrate 12 with the oxide film 21interposed between the first and second substrates thereby forming alaminated assembly 15, subjecting the laminated assembly 15 to a firstheating treatment consisting of heating at a specified temperature, sothat the first silicon substrate 14 is split at the ion-implantationzone 16 thereby manufacturing a bonded substrate 18 in which a thin SOIlayer 13 is formed on the second silicon substrate 12 with the oxidefilm 21 interposed, flattening the exposed surface of the SOI layer 13by subjecting the bonded substrate 18 to wet etching, and subjecting theresulting bonded substrate 18 to a second heating treatment consistingof heating at 900 to 1200° C. thereby enhancing the bonding strength ofthe bonded substrate 18.

The method described in claim 3 for manufacturing an SOI substrate issuitable for the manufacture of SOI substrates 11 for which moreemphasis is placed on the requirement for the quality of the crystalstructure of the SOI layer 13 than for the uniformity of thickness ofthe SOI layer 13. In the manufacture of SOI substrates according to themethod described in claim 3, since wet etching is undertaken forflattening the exposed surface of the SOI layer 13, it is possible toreduce the variation in thickness of the SOI layer 13 and render thethickness of the SOI layer 13 uniform without inflicting damage to thesurface of the SOI layer 13.

According to the embodiment of the invention, a first silicon substrateis separated at an ion-implantation zone during the first heatingtreatment to manufacture a bonded substrate comprising a thin SOI layerformed on a second silicon substrate with an oxide film interposed, andthen the bonded substrate has its surfaces flattened by wet etching sothat the exposed surface of the SOI layer is also flattened. Therefore,it is possible to remove damage on the exposed surface of the SOI layerwhich corresponds to the ion-implantation zone which may suffer fromdamage during the first heating treatment. This renders the surface ofthe SOI layer devoid of damages and its layer thickness uniform, andreduces the variation in thickness of the SOI layer.

Furthermore, according to the embodiment of the invention, a secondheating treatment consisting of heating at 750 to 900° C. in anoxidative atmosphere is introduced before the third heating treatmentconsisting of heating at 900° C. or higher to enhance the bondingstrength of a bonded substrate. This results in effective prevention ofthe development of residual damage in SOI layer into crystal defectssuch as dislocations. Also degradation of the quality of crystalstructure of the SOI layer which would otherwise result from crystaldefects can be effectively avoided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a diagram for showing the steps of a method for manufacturingan SOI substrate representing an embodiment of the invention.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Next, the preferred embodiments in the execution of the presentinvention will be described below with reference to the attacheddrawing.

As shown in FIG. 1, an SOI substrate 11 comprises a second siliconsubstrate 12 composed of silicon single crystal, and an SOI layer 13composed of silicon single crystal bonded to the second siliconsubstrate 12 with a first oxide film 21 interposed. The first oxide film21 is a silicon oxide film (SiO₂ film) having an electric insulatingproperty. In the particular embodiment shown in the figure, the secondsilicon substrate 12 has no additional oxide film. However, anadditional oxide film may be formed on the open surface of the secondsilicon substrate 12, although such additional membrane is not depictedin the figure. The SOI layer 13 has a thickness of 10 to 200 nm,preferably 10 to 70 nm. This is because: if the SOI layer 13 has athickness below 10 nm, formation of the SOI layer 13 would be difficult,while if the SOI layer 13 has a thickness over 200 nm, the variation inthickness of the SOI layer 13 would be so large that it would beimpossible to render the SOI layer 13 uniform in thickness.

The inventive method as described above for manufacturing an SOIsubstrate will be described.

First, a first silicon substrate 14 composed of silicon single crystalis prepared. Then, a first oxide film 21 (FIG. 1(a)) composed of siliconoxide (SiO₂ film) having an electric insulating property is formed notonly on the top surface of the first silicon substrate 14 but also onits bottom and side surfaces (not illustrated). The first oxide film 21has a thickness of 50 to 300 nm, preferably 100 to 200 nm. The reasonwhy the thickness of the first oxide film 21 is limited to the range of50 to 300 nm is as follow: if the first oxide film 21 has a thicknessless than 50 nm, voids would readily develop during the bonding stepbecause the void elimination due to the fluidity characteristic withoxide film heated at a high temperature would not work effectively,while if the first oxide film has a thickness over 300 nm, theuniformity of thickness of the buried oxide film would not meet therequirement for device products. The aforementioned first oxide film(SiO₂ membrane) may be formed only on the first silicon substrate by CVDinstead of by thermal oxidation.

Then, implantation of hydrogen ions into a surface of the first siliconsubstrate 14 is performed by radiating a beam of hydrogen ions at a doseof 4×10¹⁶ to 10×10¹⁶ atoms/cm² under an acceleration voltage of 20 to200 keV. Through this operation, an ion-implantation zone 16 is formedin the interior of the first silicon substrate 14 (FIG. 1(b)). Thereason why the dose is limited to the range of 4×10¹⁶ to 10×10¹⁶atoms/cm² is as follows: if the dose is below 4×10¹⁶ atoms/cm²,splitting would not occur at the ion-implantation zone 16 even when thefirst heating treatment is undertaken, while if the dose is over 10×10¹⁶atoms/cm², the irradiated superficial layer of the first siliconsubstrate 14 would be torn off of itself during the implantation ofhydrogen ions, which would readily turn into small particles on thesurface. The reason why the acceleration voltage is limited to the rangeof 20 to 200 keV is as follows: if the acceleration voltage is below 20keV, the resulting SOI layer 13 would have a too small thickness, whilefor generating an acceleration voltage over 200 keV, a specialion-implantation system must be required.

As a separate run, a second silicon substrate 12 composed of siliconsingle crystal is prepared that has the same surface areas as those ofthe first silicon substrate 14 (FIG. 1(c)). The second silicon substrate12 may be devoid of any oxide film like the one as described above. Thefirst silicon substrate 14 is laid over the second silicon substrate 12to be bonded to the latter with the first oxide film 21 interposed,thereby forming a laminated assembly 15 (FIG. 1(d)). Then, the laminatedassembly 15 is subjected to first heating treatment consisting ofheating at 400 to 800° C., preferably 450 to 600° C. for 1 to 30minutes, preferably 10 to 30 minutes in an atmosphere of nitrogen. As aresult of this operation, the first substrate 14 is split at theion-implantation zone 16 where implanted hydrogen ions are mostconcentrated, and the upper thick portion 17 is separated from the lowerthin SOI layer 13 (FIG. 1(e)). The lower SOI layer 13 is intimatelybonded over the second silicon substrate 12 with the first oxide film 21interposed, and the assembly constitutes a bonded substrate 18 (FIG.1(e)).

The bonded substrate 18 is then subjected to wet etching so as toflatten the exposed surface of the SOI layer 13 (FIG. 1(f)). Wet etchingmay be based on the use of a mixture of an oxidative agent capable ofoxidizing the surface of silicon crystal and a solution capable ofdissolving silicon dioxide. The preferred oxidative agent may include asolution obtained by dissolving ozone in an aqueous solution ofhydrofluoric acid, a mixture of hydrofluoric acid and nitric acid, andan aqueous solution of ammonia and hydrogen peroxide. Alternatively, wetetching may be based on an aqueous alkali solution capable of directlydissolving silicon. Suitable aqueous alkali solutions may includeaqueous solutions of sodium hydroxide and potassium hydroxide. Theetching system may be a batch type which allows one to deal with aplurality of substrates at one time, or a single substrate type.Regardless of whether a batch type or a single substrate type is usedfor the etching system, proper care should be taken according to theetching type: when a batch type is used, the circulation of solutionthrough the etching tank and the interval between adjacent substratesplaced in the tank should be properly adjusted to ensure the improveduniformity of thickness of substrates, and when a single substrate typeis used, the pouring of solution to each substrate and the speed forrotating the substrate should be properly adjusted, and for both thetypes, the concentration and temperature of solution should also beproperly adjusted.

The bonded substrate 18 is then subjected to the second heatingtreatment consisting of heating at 750 to 900° C., preferably at 800 to850° C. for 1 to 15 hours in an oxygen atmosphere, to reduce damagesinflicted to the SOI layer 13 (FIG. 1(h)). The reason why the heatingtemperature of the second heating treatment is limited to the range of750 to 900° C. is as follows: if the heating temperature is below 750°C., treatment would take over 15 hours which is undesirable for massproduction, while if the heating temperature is over 900° C., residualdamages in SOI layer 13 would develop into crystal defects such asdislocations which would degrade the quality of crystal structure of theSOI layer 13 of the SOI substrate 11. The second heating time is limitedto 1 to 15 hours because: if the heating time is below 1 hour,elimination of damages would be insufficient, while if the heating timeis over 15 hours, production efficiency will be wasted to no purpose.

The bonded substrate 18 with SOI layer 13 considerably devoid of damagesis then subjected to the third heating treatment consisting of heatingat 900 to 1200° C., preferably at 1050 to 1150° C. for 30 to 360minutes, preferably for 60 to 180 minutes in an atmosphere of oxygen,nitrogen, or argon, or an atmosphere comprising a mixture of thosegases, so that bondage of the SOI layer 13 to the second siliconsubstrate 12 with the first oxide film 21 interposed may be furtherenhanced (FIG. 1(j)). The reason why the heating temperature of thethird heating treatment is limited to the range of 900 to 1200° C. is asfollows: if the heating temperature is below 900° C., sufficientlystrong bondage would not be obtained, while if the heating temperatureis over 1200° C., slips would readily develop. The reason why theheating time is limited to the range of 30 to 360 minutes is as follows:if the heating time is below 30 minutes, sufficiently strong bondagewould not be obtained, while if the heating time is over 360 minutes,production efficiency will be wasted to no purpose because sufficientlystrong bondage can be obtained in a shorter time.

As a result of the second and third heating treatments, a second oxidefilm 22 is formed on the top and bottom surfaces as well as sidesurfaces (not illustrated) of the bonded substrate 18 wherein the uppersecond oxide film 22 is formed on the surface of the SOI layer 13.Immersion of the bonded substrate 18 in detergent allows the secondoxide film 22 to be etched away and the bonded substrate 18 to becleaned. The detergent preferably includes a detergent comprising anorganic acid at a concentration more than 0.1 wt % but not more than 50wt %, preferably 0.2 to 10 wt %, and hydrofluoric acid at 0.005 to 0.25wt %, preferably 0.005 to 0.10 wt %. The organic acid preferablyincludes one or two or more chosen from the group comprising citricacid, succinic acid, ethylenediamine tetraacetic acid, tartaric acid,salicylic acid, oxalic acid, acetic acid and formic acid. The reason whythe concentration of organic acid is limited to the range of more than0.1 wt % to not more than 50 wt % is as follows: if the concentration oforganic acid is below 0.1 wt %, the molecules of organic acid indetergent are so small in number that, even when free metal impuritiesderived from the second oxide film 22 disperse in detergent, they cannot react with a sufficient number of the metal impurities to formcomplexes therefrom, and will leave unreacted metal impurities todeposit again this time on the surface of the SOI layer 13, while if theconcentration of organic acid is over 50 wt %, renewed deposition ofminute particles derived from the second oxide film 22 on SOI layer 13will increase. The reason why the concentration of hydrofluoric acid islimited to the range of 0.005 to 0.25 wt % is as follows: if theconcentration of hydrofluoric acid is below 0.05 wt %, the detergentcould not have a sufficiently high sloughing effect on the second oxidefilm 22 covering the surface of the SOI layer 13, while if theconcentration of hydrofluoric acid is over 0.25 wt %, the detergent willhave a pH of less than 2, that is, become a strong acid that willinterfere with the dissociation of organic acid into ions, therebyinhibiting the complex forming activity of the latter. In addition, insuch highly acidic detergent, the charge loaded on the surface of minuteparticles therein will become positive which will promote the reneweddeposition of those particles to the surface of the SOI layer 13.

Immersion of the bonded substrate 18 having undergone the second andthird heating treatments in a detergent as described above allows thesecond oxide film 22 to be removed by virtue of hydrofluoric acid (HF)in the detergent, and minute particles and metal impurities residing onthe surfaces of second oxide film 22 as well as metal impuritiescontained in second oxide film 22 disperse into the detergent. Since thedetergent contains hydrofluoric acid at 0.005 to 0.25 wt % and organicacid at a concentration more than 0.1 wt % but not more than 50 wt %,and is an acidic solution with pH of 4 or lower, minute particles indetergent are negatively charged as is the surface of the SOI layer 13.In addition, metal impurities freely dispersed in solution react withthe molecules of organic acid to form complexes, i.e., complex metalsalts. The ions derived from those complex metal salts are negativelycharged. As a consequence, since the surfaces of minute particles andmetal impurities in solution are negatively charged as is the surface ofthe SOI layer 13, renewed or new deposition of those particles andimpurities to the surface of the SOI layer can be safely avoided. Thebonded substrate, when removed from the detergent, provides a cleanedSOI substrate 11 (FIG. 1(k)).

The depth of hydrogen ion-implantation (in terms of the level at whichthe density of implanted hydrogen ions has a peak) from the surface ofthe first silicon substrate 14 should be set after due consideration hasbeen paid to the thickness of the first oxide film 21 (50 to 300 nm, orpreferably 100 to 200 nm), etched amount due to cleaning (5 nm or less,or preferably 1 nm or less), thickness of the second oxide film 22 (20to 700 nm, or preferably 50 to 300 nm), and etched amount due to wetetching (20 to 300 nm, or preferably 50 to 200 nm). The reason why theetched amount due to wet etching is limited to the range of 20 to 300 nmis as follows: if the etched amount is below 20 nm, damages inflictedduring splitting will persist even after the high-temperature treatmentfor enhancing bondage and thus improved flatness can not be ensured,while if the etched amount is over 300 nm, etching will take such a longtime that not only production efficiency will be unduly lowered, butalso the uniformity of thickness of the SOI layer will be degraded andtoo much reaction products will be generated. The thick portion 17generated as a result of splitting has its exposed surface flattened bypolishing (FIGS. 1(g) and 1(i)). Through this operation, it is possibleto reuse the resulting thick portion 17 as a first silicon substrate 14or second silicon substrate 12 in the manufacture of SOI substrates likeSOI substrate 11.

According to the aforementioned method for manufacturing an SOIsubstrate 11, the exposed surface of the SOI layer 13 is flattened bywet etching, and thus it is possible to remove the superficial layer ofthe SOI layer 13 with damages, since the laminated assembly is split atthe ion-implantation zone 16 during the first heating treatment, andthus damages are most frequent on the exposed surface of resulting SOIlayer. The wet etching also does not inflict any additional damages onthe surface of the SOI layer 13, and reduces the variation in thicknessof the SOI layer 13 as compared with conventional CMP method, i.e.,ensures the uniformity of thickness of the SOI layer 13. According tothe inventive method for manufacturing an SOI substrate, since the thirdheating treatment is introduced subsequent to the second heatingtreatment consisting of heating to 750 to 900° C. to enhance the bondingstrength of the bonded substrate 18, it is possible to prevent crystaldefects such as dislocations from being further aggravated and thequality of the crystal structure of the SOI layer 13 from being furtherdegraded by eliminating damages from the surface of the SOI layer 13.

The amount removed due to wet etching performed in the manner asdescribed above and the duration of the second heating treatment relateto each other in terms of the quality of resulting SOI substrate, andtheir relative contributions in the manufacture of an SOI substrate 11is determined by the nature of the quality required of the SOIsubstrate. If the requirement for the high uniformity of thickness ofthe SOI layer 13 is emphasized rather than en the quality of crystalstructure of the SOI layer 13, the duration or intensity of the secondheating treatment should be emphasized at the expense of the amountremoved due to wet etching. On the contrary, if the requirement for thehigh quality of crystal structure of the SOI layer 13 is emphasizedrather than for the uniformity of thickness of the SOI layer 13, theamount removed due to wet etching should be emphasized at the expense ofthe quality of the crystal structure of the SOI layer 13. Accordingly,if the requirement for the high quality of crystal structure of the SOIlayer 13 is emphasized rather than for the uniformity of thickness ofthe SOI layer 13, the second heating treatment may be omitted. On thecontrary, if the requirement for the high uniformity of the thickness ofthe SOI layer 13 is emphasized rather than on the quality of the crystalstructure of the SOI layer 13, the step involving wet etching may beomitted.

Thus, an inventive method for manufacturing an SOI substrate from whicha step involving wet etching is omitted comprises the steps of formingan oxide film 21 at least on one surface of a first silicon substrate14, implanting hydrogen ions from the surface of the first siliconsubstrate 14 thereby forming an ion-implantation zone 16 in the interiorof the first silicon substrate 14, bonding the first silicon substrate14 over a second silicon substrate 12 with the oxide film 21 interposedthereby forming a laminated assembly 15, subjecting the laminatedassembly 15 to a first heating treatment consisting of heating at aspecified temperature, so that the first silicon substrate 14 is splitat the ion-implantation zone 16 thereby manufacturing a bonded substrate18 in which a thin SOI layer 13 is formed on the second siliconsubstrate 12 with the oxide film 21 interposed, subjecting the bondedsubstrate 18 to a second heating treatment consisting of heating at 750to 900° C. in an oxidative atmosphere thereby reducing damages inflictedto the SOI layer 13, and subjecting the resulting bonded substrate 18 toa third heating treatment consisting of heating at 900 to 1200° C.thereby enhancing the bonding strength of the bonded substrate 18.

On the other hand, an inventive method for manufacturing an SOIsubstrate from which a step involving the second heating treatment isomitted comprises the steps of forming an oxide film 21 at least on onesurface of a first silicon substrate 14, implanting hydrogen ions fromthe surface of the first silicon substrate 14 thereby forming anion-implantation zone 16 in the interior of the first silicon substrate14, bonding the first silicon substrate 14 over a second siliconsubstrate 12 with the oxide film 21 interposed thereby forming alaminated assembly 15, subjecting the laminated assembly 15 to a firstheating treatment consisting of heating at a specified temperature, sothat the first silicon substrate 14 is split at the ion-implantationzone 16 thereby manufacturing a bonded substrate 18 in which a thin SOIlayer 13 is formed on the second silicon substrate 12 with the oxidefilm 21 interposed, flattening the exposed surface of the SOI layer 13by subjecting the bonded substrate 18 to wet etching, and subjecting theresulting bonded substrate 18 to a second heating treatment consistingof heating at 900 to 1200° C. thereby enhancing the bonding strength ofthe bonded substrate 18.

EXAMPLE

Examples of the present invention will be described in detail withreference to Comparative Examples.

Example 1

As shown in FIG. 1, first a disc-shaped (outer diameter, 200 mm andthickness, 0.725 mm) first silicon substrate 14 composed of siliconsingle crystal was subjected to a heating treatment consisting ofheating at 1000° C. for 5 hours in an oxygen atmosphere, to allow afirst oxide film 21 to be formed on the top and bottom surfaces of thefirst silicon substrate 14 as well as its side surfaces. The first oxidefilm 21 has a thickness of about 150 nm. Then, implantation of hydrogenions into a surface of the first silicon substrate 14 was performed byradiating a beam of hydrogen ions at a dose of 6×10¹⁶ atoms/cm² under anacceleration voltage of 50 keV. Through this operation, anion-implantation zone 16 is formed in the interior of the first siliconsubstrate 14 (FIG. 1(b)). The depth of the ion-implantation zone 16 (interms of the level at which the density of implanted hydrogen ions had apeak) from the top surface was determined to be about 500 nm with thethickness of first oxide film 21 included. On the other hand, secondsilicon substrate 12 composed of silicon single crystal, and having thesame surface areas as those of the first silicon substrate 14 describedabove and a thickness of 0.725 mm was prepared (FIG. 1(c)). The firstsilicon substrate 14 was laid over the second silicon substrate 12 to bebonded to the latter with the oxide film 21 interposed, thereby forminga laminated assembly 15 (FIG. 1(d)). Then, the laminated assembly 15 wassubjected to first heating treatment consisting of heating at 500° C.for 30 minutes in an atmosphere of nitrogen. As a result of thisoperation, the first silicon substrate 14 was split at theion-implantation zone 16 where implanted hydrogen ions were mostconcentrated, and the upper thick portion 17 was separated from thelower thin SOI layer 13 (FIG. 1(e)). The lower SOI layer 13 wasintimately bonded to the second silicon substrate 12 with the firstoxide film 21 interposed, and the assembly constituted a bondedsubstrate 18 (FIG. 1(f)).

The bonded substrate 18 was then subjected to wet etching using amixture of HF and organic acid (tartaric acid) so that SOI layer 13 wasthinned by a thickness of 200 nm as a result of etching, and the exposedsurface of the SOI layer 13 was flattened. The bonded substrate 18 wasthen subjected to the second heating treatment consisting of heating at900° C. for 90 minutes in an oxygen atmosphere, to reduce damagesinflicted to the SOI layer 13 (FIG. 1(h)). After being removed of oxidefilms as a result of being immersed in HF solution, the bonded substrate18 with SOI layer 13 was then subjected to the third heating treatmentconsisting of heating at 1100° C. for 120 minutes in an atmosphere ofargon, so that bondage of the SOI layer 13 to the second siliconsubstrate 12 with the first oxide film 21 interposed may be furtherenhanced (FIG. 1(j)). Lastly, the bonded substrate 18 was immersed in adetergent to be cleaned which provided a cleaned SOI substrate 11 (FIG.1(k)). The SOI substrate 11 thus obtained was made Example 1. Thedetergent described above contained organic acid composed of citric acidat 0.5 wt %, and hydrofluoric acid at 0.01 wt %. The SOI layer 13 aftercleaning had a thickness of 50 nm.

Example 2

A bonded substrate 18 was subjected to wet etching so that SOI layer 13was thinned until its thickness was 300 nm. Not being subjected to asecond heating treatment consisting of heating at 900° C., the bondedsubstrate 18 was immediately subjected to a heating treatment consistingof heating at 1100° C. for 120 minutes in an atmosphere of argon. Exceptfor this alteration, the bonded substrate 18 was processed in the samemanner as in Example 1 to manufacture an SOI substrate. This SOIsubstrate was made Example 2.

Example 3

Not being subjected to wet etching, a bonded substrate 18 immediatelyreceived a second heating treatment consisting of heating at 900° C. for90 minutes in an oxygen atmosphere, and third heating treatmentconsisting of heating at 1100° C. for 120 minutes in an oxygenatmosphere in this order. Except for this alteration, the bondedsubstrate 18 was processed in the same manner as in Example 1 tomanufacture an SOI substrate. This SOI substrate was made Example 3.

Example 4

Not being subjected to wet etching, a bonded substrate 18 immediatelyreceived a second heating treatment consisting of heating at 870° C. for150 minutes in an oxygen atmosphere, and third heating treatmentperformed in the same manner as in Example 1 in this order. Except forthis alteration, the bonded substrate 18 was processed in the samemanner as in Example 1 to manufacture an SOI substrate. This SOIsubstrate was made Example 4.

Example 5

Not being subjected to wet etching, a bonded substrate 18 immediatelyreceived a second heating treatment consisting of heating at 850° C. for190 minutes in an oxygen atmosphere, and third heating treatmentperformed in the same manner as in Example 1. Except for thisalteration, the bonded substrate 18 was processed in the same manner asin Example 1 to manufacture an SOI substrate. This SOI substrate wasmade Example 5.

Example 6

Not being subjected to wet etching, a bonded substrate 18 immediatelyreceived a second heating treatment consisting of heating at 800° C. for15 hours in an oxygen atmosphere, and third heating treatment performedin the same manner as in Example 1. Except for this alteration, thebonded substrate 18 was processed in the same manner as in Example 1 tomanufacture an SOI substrate. This SOI substrate was made Example 6.

Example 7

Not being subjected to wet etching, a bonded substrate 18 immediatelyreceived a second heating treatment consisting of heating at 750° C. for30 hours in an oxygen atmosphere, and third heating treatment performedin the same manner as in Example 1. Except for this alteration, thebonded substrate 18 was processed in the same manner as in Example 1 tomanufacture an SOI substrate. This SOI substrate was made Example 7.

Comparative Example 1

Not being subjected to wet etching, a bonded substrate 18 immediatelyreceived a second heating treatment consisting of heating at 1000° C.for 12 minutes in an oxygen atmosphere, and third heating treatmentperformed in the same manner as in Example 1. Except for thisalteration, the bonded substrate 18 was processed in the same manner asin Example 1 to manufacture an SOI substrate. This SOI substrate wasmade Comparative example 1.

Comparative Example 2

Not being subjected to wet etching, a bonded substrate 18 immediatelyreceived a second heating treatment consisting of heating at 950° C. for30 minutes in an oxygen atmosphere, and third heating treatmentperformed in the same manner as in Example 1. Except for thisalteration, the bonded substrate 18 was processed in the same manner asin Example 1 to manufacture an SOI substrate. This SOI substrate wasmade Comparative example 2.

Comparison Test and Evaluation

HF defects on SOI substrate in Examples 1 to 7 and Comparative examples1 and 2 were observed by microscopy and their density was measured. Theresults are listed in Table 1. TABLE 1 Second heating treatment, Wetetching, temperature & Density of HF removal amount time defects [/cm²]Example 1 Done, 200 nm Done, 900° C., 0.1 90 minutes Example 2 Done, 300nm Undone 0.1 or less Example 3 Undone Done, 900° C., 0.2 90 minutesExample 4 Undone Done, 870° C., 0.1 or less 170 minutes Example 5 UndoneDone, 850° C., 0.1 or less 190 minutes Example 6 Undone Done, 800° C.,0.1 or less 15 hours Example 7 Undone Done, 750° C., 0.1 or less 30hours Comparative Undone Done, 1000° C., 1.6 example 1 12 minutesComparative Undone Done, 950° C., 1.0 example 2 30 minutes

As is obvious from the results shown in Table 1, for the SOI substratesrepresented by Examples 1 and 2 in which wet etching was applied to abonded substrate and by Example 1 and Examples 3 to 7 in which a secondheating treatment consisting of heating at 750 to 900° C. was applied,the density of HF defects was reduced to 0.2/cm² or less. In contrast,for SOI substrates represented by Comparative examples 1 and 2 in whicha heating treatment consisting of heating at a temperature over 900° C.was applied to a bonded substrate, the density of HF defects waselevated to 1.0/cm² or more. This merit characteristically observed inExamples 1 to 7 may be ascribed to wet etching or second heatingtreatment consisting of heating at 750 to 900° C. which was exclusivelyapplied to bonded substrates designed to manufacture Examples. Thisindicates that the inventive method effectively achieves the object.

1. A method for manufacturing an SOI substrate comprising the steps of:forming an oxide film (21) at least on one surface of a first siliconsubstrate (14); implanting hydrogen ions from the surface of the firstsilicon substrate (14) thereby forming an ion-implantation zone (16) inthe interior of the first silicon substrate (14); bonding the firstsilicon substrate (14) over a second silicon substrate (12) with theoxide film (21) interposed between the first and second substratesthereby forming a laminated assembly (15); subjecting the laminatedassembly (15) to a first heating treatment consisting of heating at aspecified temperature, so that the first silicon substrate (14) is splitat the ion-implantation zone (16) thereby manufacturing to produce abonded substrate (18) in which a thin SOI layer (13) is formed on thesecond silicon substrate (12) with the oxide film (21) interposedbetween the SOI layer and the second substrate; flattening the exposedsurface of the SOI layer (13) by subjecting the bonded substrate (18) towet etching; subjecting the bonded substrate (18) to a second heatingtreatment consisting of heating at 750 to 900° C. in an oxidativeatmosphere thereby reducing damage to the SOI layer (13); and subjectingthe resulting bonded substrate (18) to a third heating treatmentconsisting of heating at 900 to 1200° C. thereby enhancing the bondingstrength of the bonded substrate (18).
 2. A method for manufacturing anSOI substrate comprising the steps of: forming an oxide film (21) atleast on one surface of a first silicon substrate (14); implantinghydrogen ions from the surface of the first silicon substrate (14)thereby forming an ion-implantation zone (16) in the interior of thefirst silicon substrate (14); bonding the first silicon substrate (14)over a second silicon substrate (12) with the oxide film (21) interposedbetween the first and second substrates thereby forming a laminatedassembly (15); subjecting the laminated assembly (15) to a first heatingtreatment consisting of heating at a specified temperature, so that thefirst silicon substrate (14) is split at the ion-implantation zone (16)thereby manufacturing a bonded substrate (18) in which a thin SOI layer(13) is formed on the second silicon substrate (12) with the oxide film(21) interposed between the SOI layer and the second substrate;subjecting the bonded substrate (18) to a second heating treatmentconsisting of heating at 750 to 900° C. in an oxidative atmospherethereby reducing damages to the SOI layer (13); and subjecting theresulting bonded substrate (18) to a third heating treatment consistingof heating at 900 to 1200° C. thereby enhancing the bonding strength ofthe bonded substrate (18).
 3. A method for manufacturing an SOIsubstrate comprising the steps of: forming an oxide film (21) at leaston one surface of a first silicon substrate (14); implanting hydrogenions from the surface of the first silicon substrate (14) therebyforming an ion-implantation zone (16) in the interior of the firstsilicon substrate (14); bonding the first silicon substrate (14) over asecond silicon substrate (12) with the oxide film (21) interposedbetween the first and second substrates thereby forming a laminatedassembly (15); subjecting the laminated assembly (15) to a first heatingtreatment consisting of heating at a specified temperature, so that thefirst silicon substrate (14) is split at the ion-implantation zone (16)thereby manufacturing a bonded substrate (18) in which a thin SOI layer13 is formed on the second silicon substrate (12) with the oxide film(21) interposed between the SOI layer and the second substrate;flattening the exposed surface of the SOI layer (13) by subjecting thebonded substrate (18) to wet etching; and subjecting the resultingbonded substrate (18) to a second heating treatment consisting ofheating at 900 to 1200° C. thereby enhancing the bonding strength of thebonded substrate (18).
 4. The method of claim 1 wherein the first oxidefilm has a thickness in the range from 50 to 300 nm.
 5. The method ofclaim 1 wherein the hydrogen ions are implanted by radiating the firstsilicon substrate with a beam of hydrogen ions at a dose of 4×10¹⁶ to10×10¹⁶ atoms/cm² under an acceleration voltage of 20 to 200 kev.
 6. Themethod of claim 1 wherein the first heating treatment is carried out ata temperature of from 400 to 800° C. for 1 to 30 minutes.
 7. The methodof claim 1 wherein the second heating treatment is carried out for 1 to15 hours.
 8. The method of claim 1 wherein the third heating treatmentis carried out for 30 to 360 minutes.
 9. The method of claim 1 whereinthe removal of the oxide film after the third heating treatment iscarried out by immersing the bonded substrate in a detergent whichcomprises from 0.1 to 50 wt. % of an organic acid and 0.005 to 0.25 wt.% hydrofluoric acid.
 10. The method of claim 1 wherein the thickness ofthe oxide film after the third heating treatment prior to its removal isfrom 20 to 700 nm and after its removal is from 20 to 300 nm.
 11. Themethod of claim 2 wherein the first oxide film has a thickness in therange from 50 to 300 nm.
 12. The method of claim 3 wherein the firstoxide film has a thickness in the range from 50 to 300 nm.
 13. Themethod of claim 2 wherein the hydrogen ions are implanted by radiatingthe first silicon substrate with a beam of hydrogen ions at a dose of4×10¹⁶ to 10×10¹⁶ atoms/cm² under an acceleration voltage of 20 to 200kev.
 14. The method of claim 2 wherein the first heating treatment iscarried out at a temperature of from 400 to 800° C. for 1 to 30 minutes.15. The method of claim 2 wherein the second heating treatment iscarried out for 1 to 15 hours.
 16. The method of claim 2 wherein thethird heating treatment is carried out for 30 to 360 minutes.
 17. Themethod of claim 1 wherein the thickness of the oxide film after thethird heating treatment prior to its removal is from 20 to 700 nm andafter its removal is from 20 to 300 nm.
 18. The method of claim 3wherein the hydrogen ions are implanted by radiating the first siliconsubstrate with a beam of hydrogen ions at a dose of 4×10¹⁶ to 10×10¹⁶atoms/cm² under an acceleration voltage of 20 to 200 kev.
 19. The methodof claim 3 wherein the first heating treatment is carried out at atemperature of from 400 to 800° C. for 1 to 30 minutes.
 20. The methodof claim 3 wherein the second heating treatment is carried out for 1 to15 hours.
 21. An SOI substrate made by the method of claim
 1. 22. An SOIsubstrate made by the method of claim
 2. 23. An SOI substrate made bythe method of claim 3.